Acid-fading inhibition using dibenzylethylenediamine



Patented Mar. 27, 1951 .UNITED 4s'lA-Tlrf laPA'l`;.ll-NT OFFICE AcIn-FADING INHIBITIQNUSINGDIBEN- zYi.ETHYLENEDIAMINE Victor S. Salvin, Irvington, and John R. Adams,

Jr., Summit, N. J., assignors to Celanese Corlporation of America, a corporation of Delaware a NoDrawing. Application July 3, 1948,

lSerial No.',3 7v,093 s Claims.

This invention relateslto the treatment of dyed organic derivative of cellulose textile materials, anderelates' lmore particularly to the Atreatment lof organic derivative of cellulose textile' mate- ;-rials "dyed with dyestuls vhaving a tendency ,to fiadewhen exposedto an acid atmosphere, Wherefbv said fading is inhibited;`

` An object oflthis invention is toprovide an im- ,.pro'ved process -ior the treatment .of Vcolored Yce1- llulos'e acetate or other organicderivative of cellulose 4textile materials which have been dyed @with colors which are not ordinarily fast toacid Ifumes Awhereby the resistance of said dyed textile `materials to acid fading is substantially improved. Another object ofthis-invention is the provision ,ofdyed cellulose acetate or other organic derivavacidV fading AVinhibitors incorporated therein which v have-a substantive Laiinity for said cellulose acetate or otherorganic derivative of cellulose tex- -tile materials and which do not dissolve when said treated materialsare exposed to light and to acid `fumes.

i Other objectsYof-thisinvention Willappear from thefollowing detailed description. Inthe coloration of textile materials it is very `desirable that the colors produced on the materialsbe as fast as possible to light, washing, and to other agencies such as acid fumes. Many dyestuffsyield on organic' derivative of celulose materials ydesirable colors whichare fast to washing-but these colors often suffer from a lack oi` Affastness toacidfumes. When fabrics to which these `dyestufs havebeen applied arev exposed to acid fumess"uch" as, .forfexampe the products of combustion of'coahgasjetc., the color undergoes a change in shadefljh'is'change is usually referred to as acid fading. The change which .occurs.may be .adulling of the brightness of the shade in some instances, and in others there'may bea denite change in color. This undesirable effect is` .frequently observed in the case of many anthraquinone dyestus which yield valuable blue colors on organic derivative of cellulose ma- ,terialsV When fabrics dyed with these colors are exposed gtoacid fumesthe colors change from a pure blue shade to one having a reddish cast. n' .continued exposure vtothe acid fumes the blue color `may even change to Aa pink color. Such changes'naturall'y restrict Ithe range of usefulness .oi :these .,dyestuffs. Accordingly, methods Vof in- (c1. s-sn which have been dyed with dyestufs which are not'iast" to the action of acid vfumes maybe substantially'ii'nproved if'there `is applied 'to said `dyedfcellulse` acetateor other organic derivative fof cellulose textile material an amineselected lfrom the group consisting of diphenylbenz'amidine l:and dibenavlethylenediamine." Each of `said lamines have a :substantive affinity for cellulose 'acetate or other organic derivative of cellulose and 'are water vinsoluble so'that they are vu'r'iaiffected ley/"washing.4 Furthermore. they are stron'gf ly resistant to any changes under the actionof acid vfumes and, accordingly, do not'dis'color.

"While said amine ac id'fading inhibitingagents may be 'applied to the dyedcellulose acetate or other organic derivative of cellulose textile mate-- rial in the iorrnof 'a' solution in a solvent such 'as aqueous 'alcohol,"'diacetone alcohol, or' other scl- 'ven't whichf does not have an 'undesirable' solvent Yactionen'theorg'anic derivative of cellulose mate'- r'al, 1511mesfedrentaeeeus results are blfaed when melamine, empleadas applied ,in the form foi a stabilewaqueous emulsion consisting of a 4solution ofsaid amine lin aWaterQ- insoluble organic solvent, for exampleQtoluene containing""'some "ethyl alcohohvvhichy is dispersed in `v'vater"with thes'aid of suitable dispersing agents to form the desired emulsion, thedropletsfuof the water-,insel uble solvent solution of theinhibitingag'ent comprisinggtbe disperse phase y*andthe Water 'thel'cof'ntinuous phase ofthe emulsion.

ThemiilSQn 0r Solution'of inhibiting agnis preferably appliedto `the dyedl organic derivative of cellulose'textilematerial' bypaddirig operations, rtlfie nipo-f the padding mangle being sc adjusted that"A suicient liquid is retained on r the fabric to deposit in a'uniiorm fashion thereon from 0.3 to 1.0% on the Weight of the fabric of the inhibiting agent after kthe liquid vehicle is removedand the treated ,fabric is dried. Drying of the paddedfabric may beA conveniently effected at altemperatu're of 70 to 150 C., preferably about C., ,the treated fabric being exposed to vsaid temperatureuntil the liquid vpresent is evaporated, usuallyfinfrorn about to 20 minutes. When .applying diphenylbenzamidine or ,dlvbenzylethylenediamine to the dyed textile material V in Aemulsion form, ,the amine employed ispreferably dissolved in a water-insoluble `crganicliquid solvent therefor containinga pluralityyofdispersing agents at least one ofwhich isa Water-soluble anionic surface active agent and -.one which is a Water-insoluble,l but oilsoluble Vnon-ionic surface active agent, and the organic solution obtained then dispersed in water Withagitation'to form the desired stable aqueous emulsion; Y The emulsion thus obtained comprises vadispersion 'of droplets'of an vorganic solution of the inhibitor in water. The :Water-insoluble but oil-Soluble vdispersing :agent stabilizes the disperse phase of the emulsion and acts as an auxiliary solvent for the amine inhibitor in the organic solvent While the Water-soluble, anionic surface active agent stabilizes the emulsion of the Water-insoluble droplets in the aqueous, continuous phase. In treating the text'le material, the aqueous emulsion is preferably applied, as stated, by padding operations, although any other convenient method of appication may be employed. The method of preparing the novel emulsions is more particularly described in co-pending application S. No. 37,094, filed July 3, 1948.

The application of diphenylbenzamidine or dibenzylethylenediamine as acid fading inhibitors on dyed textile materials and, particularly, in the specific emulsion form in which We preferably apply said inhibitors yields a degree of -protection which is quite outstanding. Not only is the degree of protection obtained superior to that obtained when the inhibiting agents are applied, for example, simultaneously with the dyes, but it is also quite superior to the results obtained even when arylamines closely related to said aforementioned amines are employed. We have found that in the case of both dinhenvlbenzamidine and dibenzylethylenediamine although there are free amino groups present there is a complete absence of the yellowing normally produced when dyed textile materials containing inhibitors having free primary or secondary amino groups are exposed to acid fumes. Consequently, no undesirable modication in shade results on employing either diphenylben'amidine or dibenzylethylenediamine as an inhibiting agent on the dyed textile materials even after extended exposure of said textile materials to acid fumes. This is quite surprising since many compounds closely related in structure to diphenylbenzamidine and dibenzylethvlenediamine discolor appreciably when textile materials having said closely related compounds applied thereto as acid fading inhibitors are exposed to acid fumes. Furthermore, textile materials treated by said emulsion method with dibenzylethylenediamine or dinhenylbenzamidine retain their resistance to acid fading even after said materials are Washed or subjected to dry cleaning operations.

In order further to illustrate our invention, but Without being limited thereto, the following examples are given:

Eample I A solution of dispersing agents is formed by dissolving parts by weight of completely sulfonated glyceryl triricinoleate. a Water-soluble anionic surface active agent, 10 parts by Weight of Water miscible, non-ionic monolauryl ether of a polyethylene glycol of the general formula HOCH2CH2-O(CH2CH2O)n-C12H25, wherein TL is 2 to 10, 10 parts by weight of the dioleate of a polyethylene glycol such as dodecaethylene glycol Which is water-insoluble but oil soluble and non-ionic in character, and 10 parts by weight of dioxan in 60 parts by weight of toluene. 10 parts by weight of dibenzylethylenediamine are dissolved in 30 parts by weight of the above solution by warming the latter to 'l5 to 80 C. and the resulting solution then poured into 970 parts by weight of Water with stirring. An emulsion of organic liquid droplets in WaterV is formed by further stirring at high speed. The average particle size of the amine is thus reduced to about 1 micron or less.

A cellulose acetate fabric dyed in a blue shade with 1r4-dimethylamino-anthraquinone is padded with the above emulsion, the nip of the padding mangle being so adjusted that the fabric retains an equal Weight of liquid. The impregnated fabric is then dried by heating at to C. for about 15 minutes. About 1% on the weight of the dyed fabric of dibenzylethylenediamine is thus incorporated therein. The treated dyed fabric has a resistance to acid fading of 2 units in accordance with the standard A. A. T. C. C. test While untreated dyed fabric has an acid fading resistance of only 0 units. The treated fabric retains its resistance to acid fading even after being washed or drycleaned.

Example II An aqueous emulsion containing 1% by Weight of diphenylbenzamidine is prepared in the manner described in Example I. When padded onto a cellulose acetate fabric dyed in a blue shade With l:4-dimethylamino-anthraquinone so as to deposit uniformly thereon 1% by weight of diphenylbenzamidine, the treated dyed fabric obtained exhibits a resistance to acid fading of 1.5 units in accordance with the standard A. A. T. C. C. test. As indicated above, untreated dyed fabric has a resistance to acid fading of only 0 units.

Example III To a dyebath comprising an aqueous disper sion containing 0.2% by Weight of 1,4-di-methylamino-anihraquinone on the fabric to be dyed is added suicient diphenylbenzamidine dispersed with. the aid of sodium lignosulfonate so that the dycbath contains 1% by Weight of the inhibiting agent based on the fabric. The dyebath is raised to ateinperature of about 30 to 85 C. and a cellulose acetate fabric is immersed therein for about 1 hour. The fabric is dyed in a blue shade by this treatment and also absorbs about 0.6% by Weight based on the fabric of the diphenylbenzamidine. On exposure of the dyed fabric to acid fumes for one unit in accordance with the standard A. A. T. C. C. test, practically no change in shade is observed While after 2 units of exposure the dyed fabric undergoes a slight greying. Cellulose acetate fabric dyed in a similar manner With said dyestuff but without employing diphenylbenzamidine as an acid-fading inhibitor fades to a reddish-purple color after 1 unit of exposure and compleely to a pink color after 2 units of exposure. The dyed fabric containing the inhibitor retains its resistance to acid-fading even after Washing and dry-cleaning.

Example IV A blue cellulose acetate fabric which has been dyed to a blue shade with 0.3% of l-amino-fianilido anthraquinone is padded with a solution of dibenzylethylenediamine in an aqueous alcohol. The composition of the aqueous alcohol is 65% of ethyl alcohol and 35% Water by Weight. The concentration of the dibenzylethylenediamine in its aqueous alcohol solution is 1% of the Weight of the aqueous alcohol solution. The nip of the padding mangle is adjusted so that the fabric contains an equal weight of liquid after it passes through the padding bath at 25 C. The impregnated fabric is then dried to remove the solvent. About 1% of the Weight of the dyed fabric of dibenzylethylenediamine is incorporated in this manner Within the fabric. Subsequent washing or dry cleaning does not remove the dibenzylethylenediamine and a protectivel action against gas fading is not lowered by the washing or dry cleaning treatments. The treated dyed fabric has a resistance to acid fading of two units in accordance with the standard A. A. T. C. C. test, while untreated dyed fabric has an acid fading resistance of 0 units.

,While our invention has been more particularly described in connection with the treatment of textile materials having a basis of cellulose acetate, equally satisfactory results are obtained in the treatment of textile materials having a basis of other organic derivatives of cellulose. Examples of other organic derivatives of cellulose are cellulose esters such as cellulose propionate, cellulose butyrate, cellulose acetate-butyrate and cellulose acetate-propionate and cellulose ethers such as ethyl cellulose and benzyl cellulose.

It is to be understood that the foregoing detailed description is given merely by Way of illustration and that many variations may be made therein without departing from the spirit of our invention.

Having described our invention, what we desire to secure by Letters Patent is:

1. Process for improving the fastness of colorations on dyed organic derivative of cellulose textile material to acid fading, which comprises treating said dyed organic derivative of cellulose textile material with dibenzylethylenediamine.

2. Process for improving the fastness of colorations on dyed cellulose acetate textile material to acid fading, which comprises treating said dyed cellulose acetate textile material with dibenzylethylenediamine.

3. Process for improving the fastness of colorations on dyed organic derivative of cellulose textile material to acid fading, which comprises treating said dyed organic derivative of cellulose textile material with a stable emulsion comprising a solution in a water-insoluble organic solvent of dibenzylethylenediamine, which solution is dispersed in water.

4. Process for improving the fastness of colorations on dyed cellulose acetate textile material to acid fading, which comprises treating said dyed cellulose acetate textile material with a stable emulsion comprising a solution in a water-insoluble organic solvent of dibenzylethylenediamine, which solution is dispersed in water.

5. Process for improving the fastness of colorations on dyed organic derivative of cellulose textile materials to acid fading, which comprises treating said dyed organic derivative of cellulose textile materials with a stable emulsion comprising a solution of dibenzylethylenediamine in toluene dispersed in water.

6. Process for improving the fastness of colorations on dyed cellulose acetate textile materials to acid fading, which comprises treating said dyed cellulose acetate textile materials with a stable emulsion comprising a solution of dibenzylethylenediamine in toluene dispersed in water.

7. Process for improving the fastness of colorations on dyed cellulose acetate textile materials to acid fading, which comprises treating said dyed cellulose acetate materials with a stable emulsion comprising a solution of dibenzylethylenediamine in toluene and containing some dioxan dispersed in water whereby from 0.3 to 1.0% by weight of said amine is applied thereto and then drying the treated material.

8. Process for improving the fastness of colorations on dyed cellulose acetate textile materials to acid fading, which comprises treating said dyed cellulose acetate materials with a stable emulsion comprising a solution of dibenzylethylenediamine in toluene containing some ethyl alcohol dispersed in Water whereby from 0.3 to 1.0% by weight of said amine is applied thereto and then drying the treated textile material.

9. Process for improving the fastness of colorations on'dyed cellulose acetate textile material to acid fading, which comprises treating said dyed cellulose acetate textile material with a stable emulsion comprising a solution in a Water-insoluble organic solvent of dibenzylethylenediamine dispersed in water, said emulsion being formed by dissolving a plurality of dispersing agents in the organic solvent employed, at least one of which dispersing agents is a watersoluble anionic surface active agent and one a water-insoluble but oil-soluble non-ionic surface active agent, adding the amine thereto, dissolving it therein and dispersing the resulting organic solution in water.

10. Process for improving the fastness of colorations on dyed cellulose acetate textile materials to acid fading, which comprises treating said dyed cellulose acetate textile materials with a stable emulsion comprising a solution of dibenzylethylenediamine in toluene dispersed in Water, said emulsion being prepared by dissolving sulfonated glyceryl ricinoleate, a water-insoluble, oil-soluble dioleate of a poly-ethylene glycol and the mono-lauryl ether of a polyethylene glycol in toluene, adding the amine thereto, dissolving it therein, and dispersing the resulting organic solution in water.

11. Dyed organic derivative of cellulose textile material dyed with a dyestuff normally tending to fade on exposure to acid fumes and having incorporated therein dibenzylethylenediamine.

12. Dyed cellulose acetate textile material dyed with a dyestuff normally tending to fade on exposure to acid fumes and having incorporated therein dibenzylethylenediamine.

13. Dyed cellulose acetate textile material dyed with a dyestuff normally tending to fade on exposure to acid fumes and having incorporated therein from 0.3 to 1.0% by weight of dibenzylethylenediamine.

VICTOR S. SALVIN. JOHN R. ADAMS, JR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,69U,481 Ellis Nov. 6, 1928 1,723,271 Ellis Apr. 28, 1931 1,803,008 Ellis Oct. 18, 1932 1,883,351 Dreyfus Oct. 18, 1932 2,017,119 Ellis Oct. 15, 1935 2,083,122 Olpin June 8, 1937 2,869,122 Giles Feb. 13, 1945 2,416,380 Collie Feb..25, 1947 FOREIGN PATENTS Number Country Date 361,362 Great Britain Nov. 16, 1931 OTHER REFERENCES Jour. of the Am. Pharm. Assoc. (Scientific edition), for February 1945, pages 56, 57, 58.

"Atlas Spans and Tweens, published by Atlas Powder Co., Wilmington, Del., November 1942, pages 5 and 8.

Rayon Textile Mo. for June, 1945, page 97. 

1. PROCESS FOR IMPROVING THE FASTNESS OF COLORATIONS ON DYED ORGANIC DERIVATIVE OF CELLULOSE TEXTILE MATERIAL TO ACID FADING, WHICH COMPRISES TREATING SAID DYED ORGANIC DERIVATIVE OF CELLULOSE TEXTILE MATERIAL WITH DIBENZYLETHYLENEDIAMINE. 